JPH11295900A - Photosensitive resin laminate and its production - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain excellent adhesive property and dimensional stability even in a batch-type developing machine using strong rotating brushes, and to enable water-based development by forming, successively from the lower layer, an elastic layer, adhesive layer, base coating layer and photosensitive resin layer. SOLUTION: A base coating layer comprising a thermoplastic elastomer is formed under the photosensitive resin layer, and further, an adhesive layer is formed between the base coating layer and the support. Namely, the photosensitive resin laminate used consists of, from the lower layer, a support adhesive layer, base coating layer and photosensitive resin layer. As for the thermoplastic elastomer used, for example, a polystyrene polymer block, polyester polymer block such as polyethylene terephthalate and polytrimethylene terephthalate, and a conjugate diene compd. block such as polybutadiene, polyisoprene and polychloroprene can be used.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a photosensitive resin laminate and a method for producing the same. More specifically, by providing an undercoat layer on the photosensitive resin layer and further providing an adhesive layer between the undercoat layer and the support, excellent adhesion and dimensional stability can be obtained. The present invention relates to a photosensitive resin laminate which does not peel off between the support and the photosensitive resin layer even during the development processing of the above, and is particularly suitable for a water-based developable flexographic printing plate.

[0002]

2. Description of the Related Art In general, a photosensitive resin laminate for a flexographic printing plate is obtained by laminating a photosensitive resin layer having an appropriate elastic surface on a support. Envelopes, labels, paper bags, heavy bags, wrapping paper,
It is used as a relief material for printing on corrugated balls, paper containers and the like.

[0003] In particular, in the case of printing on heavy bags, wrapping paper, corrugated balls, etc., the photosensitive resin layer is generally thickened because the surface smoothness of the material to be printed is poor and the ink followability is poor. For example, for plate materials such as heavy bags and corrugated balls, usually 4 mm or more,
Most are used as a plate thickness of about 7 mm. However, in order to obtain the plate thickness only with the photosensitive resin layer, there are many problems such as economical production, fatigue of the developing solution, and the like.
m, and the remaining 4 mm is bonded as a support with a rubber sheet material such as raw rubber, vulcanized rubber or synthetic rubber, a soft salt sheet material, urethane foam, sponge or the like as a support and a total thickness of 7 mm. It is supplied as a printing plate material.

On the other hand, conventionally, a photosensitive flexographic plate material which can be developed with a halogen-based organic solvent is used, and as a method of bonding, a method of removing the flexographic plate support, exposing the photosensitive resin layer to back exposure, and bonding with a good solvent. (Tokuhei 4-6862
No. 0), a method of treating the surface to be bonded with an organic active halogen-containing compound and bonding the same (Japanese Patent Publication No. 5-56374);
A method is disclosed in which a photocurable composition is interposed between a photosensitive flexographic plate and a rubber sheet material to bond the photosensitive flexographic plate by exposure (Japanese Patent Publication No. 60-16997).

In accordance with recent environmental regulations, water-based photosensitive flexographic printing plate materials have been replaced with photosensitive flexographic printing plate materials developable with the above-mentioned halogen-based organic solvents.
For example, Japanese Patent Application Laid-Open Nos.
No. 3055, JP-A-63-8648, JP-A-1-10
8542, JP-A-2-175702, JP-A-4-3
No. 162, JP-A-1-219735 and JP-A-2-30
5805, JP-A-3-228060, JP-A-6-2
Plate materials using the photosensitive resin compositions disclosed in JP 89610, JP-A 7-114180 and the like are being used.

As a method of adhering the water-based developable photosensitive flexographic printing plate material to a support, there is provided a photosensitive resin in which an adhesive layer mainly composed of a polymer resin / reactive monomer is provided below a water-based developable photosensitive resin. Flexographic plate (Japanese Unexamined Patent Publication No.
97369). Conventionally, as a bonding method, there are a method using a commercially available adhesive, a method using a double-sided adhesive tape, and the like.

[0007]

However, in the case of a water-based developable photosensitive resin in particular, since the photosensitive resin composition has a phase-separated structure or a structure close to the phase-separated structure in order to enable water-based developability, the adhesiveness is reduced. The cohesive force to obtain, and further, the adhesive force is poor, and even more, the one formed by exposing and hardening the back surface of the photosensitive resin to form a floor has a remarkable decrease in the cohesive force and the adhesive force, and the method and the method described above provide the adhesiveness. There is a problem that cannot be solved. Further, in the method, since the properties of the photosensitive flexographic plate affect the photocurable adhesiveness, the method is not general and may not provide sufficient adhesiveness. In the method, the adhesive layer is partially cured at the time of back exposure for forming the floor of the photosensitive resin layer, the solubility by the organic solvent is reduced, and the adhesiveness varies. In some cases, the adhesiveness is not endurable. At the present time, there is no commercially available adhesive capable of obtaining sufficient adhesiveness in the method, and the method generally has a problem that the method is expensive and a problem that air bubbles are mixed in the bonding operation to deteriorate printability.

[0008]

SUMMARY OF THE INVENTION Accordingly, the present invention has been made under such circumstances, and is particularly effective when applied to a water-based developable printing plate for flexographic printing. Is a water-based developable photosensitive resin laminate that can provide excellent adhesion and dimensional stability even during development processing with a batch type developing machine using a particularly strong rotating brush or an automatic developing machine that supports wide width. To provide.

The inventors of the present invention have conducted intensive studies to solve the above-mentioned problems. As a result, the undercoat layer made of a thermoplastic elastomer is provided below the photosensitive resin layer, and the undercoat layer and the support are provided together. It was found that excellent adhesiveness and dimensional stability were obtained by interposing an adhesive layer between them, and the present invention was finally completed. That is, the present invention provides (1) a photosensitive resin laminate comprising at least a support, an adhesive layer, an undercoat layer, and a photosensitive resin layer in order from the lower layer, and (2) the undercoat layer formed of a thermoplastic elastomer. The photosensitive resin laminate according to (1), wherein the solvent content is 2% by weight or less, and (3) a photosensitive resin layer having an undercoat layer and a support having an adhesive layer. 2. The method for producing a photosensitive resin laminate according to claim 1, wherein the body is laminated so that the undercoat layer and the adhesive layer are in contact with each other.

In the present invention, examples of the thermoplastic elastomer used as the undercoat layer of the photosensitive resin layer include polystyrene polymer blocks, polyethylene terephthalate, polytrimethylene terephthalate, and polytetramethylene. Polyester polymer blocks such as terephthalate, conjugated diene compound blocks such as polybutadiene, polyisoprene, polychloroprene, etc .; aliphatic polyester polymer blocks such as polycaprolactone; poly (diethylene glycol, Examples include aliphatic polyether polymer blocks such as triethylene glycol and tetraethylene glycol), and elastomeric block copolymers such as ethylene-propylene copolymer block and ethylene-acrylic acid copolymer block. And styrene Styrene-butadiene random copolymer comprising monomeric units of butadiene, elastomeric acrylonitrile-butadiene random copolymers consisting of monomeric units of acrylonitrile and butadiene - shaped random copolymers. Other examples include polybutadiene, polyisoprene, natural polyisoprene, and the like, and these may be used alone or in combination.

The structure of the block copolymer comprising the hard segment A and the soft segment B is not particularly limited. For example, a diblock of the general formula AB, a triblock of ABA, (A -B) n multi-blocks, (A-
B) n · X star type block (n is an integer of 1 to 10)
Among these, in the present invention, a polystyrene block copolymer having a styrene content of 15% or more is preferable, and specifically, styrene.
Butadiene / styrene block copolymer, styrene / isoprene / styrene block copolymer, hydrogenated styrene /
Butadiene / styrene block copolymer, styrene / ethylene / butylene / styrene block copolymer, styrene / ethylene / propylene / styrene block copolymer, epoxy-modified styrene / butadiene / styrene block copolymer, and the like. It is preferable to use them alone or in combination.

The undercoat layer may contain a photopolymerizable ethylenically unsaturated monomer in addition to the thermoplastic elastomer. As the photopolymerizable ethylenically unsaturated monomer,
Aromatic vinyl monomers such as styrene, vinyltoluene, chlorostyrene, vinylnaphthalene, vinylanthracene, divinylbenzene and trivinylbenzene; ethylenically unsaturated nitrile monomers such as acrylonitrile and methacrylonitrile; ethyl acrylate, acrylic N-amyl acid, ethylhexyl acrylate, octyl acrylate,
Glycidyl acrylate, propyl methacrylate, isoamyl methacrylate, hexyl methacrylate, ethylhexyl methacrylate, hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxyethyl methacrylate, glycidyl methacrylate, trimethylolpropane triacrylate, 1,4-butane Diol diacrylate, propylene glycol diacrylate, 1,6
-Hexanediol dimethacrylate, 1,9-nonanediol diacrylate, methoxypropylene glycol methacrylate, methoxypropylene glycol acrylate, diethyl maleate, dimethyl itaconate, and other ethylenically unsaturated carboxylic acid ester monomers.

When a subbing layer made of such a thermoplastic elastomer is laminated on a photosensitive resin layer, the thermoplastic elastomer layer has a solvent content of 0.1% by weight to 2% by weight, preferably 0.1% by weight. % To 1.5% by weight, more preferably 0.1% to 1.5% by weight.
Preferably it is in the range from 5% by weight to 1.0% by weight. If the solvent content exceeds 2% by weight, stickiness occurs in the undercoat layer, and this is rather a cause of lowering the adhesiveness to the photosensitive resin layer, which is not preferable. Also 0.
If the amount is less than 1% by weight, the absolute amount of the residual solvent for enhancing the compatibility between the photosensitive resin layer and the undercoat layer is insufficient, and thus the adhesiveness cannot be sufficiently obtained.

As a method for obtaining the material comprising the undercoat layer of the present invention, a coating solution prepared by dissolving a thermoplastic elastomer in an organic solvent on a support having a release agent layer in advance is used.
Coating using a coating machine such as a tar coater, a bar coater, a reverse roll coater, etc., and the solvent content after drying is 0.1% by weight.
A material having an undercoat layer is obtained by treating with a dryer in which the temperature of the dryer, the residence time of the drying zone, the gradient temperature and the like are set so as to be 2% by weight. Further, it is preferable that the undercoat layer is covered with a separate material until it is laminated with the photosensitive resin in order to protect the undercoat layer. As the separating material, polyethylene, release paper or the like is usually used, and preferably, embossed polyethylene is preferable in terms of handleability and release properties.

When the undercoat layer is obtained, the organic solvent for obtaining the coating liquid of the thermoplastic elastomer is not particularly limited, and examples thereof include hydrocarbons such as toluene, cyclohexane, benzene and xylene. Kind, 1,1,1
General-purpose organic solvents such as halogenated hydrocarbons such as trichloroethane, carbon tetrachloride, chloroform and chlorobenzene, ethers such as dioxane, ketones such as methyl ethyl ketone and esters such as ethyl acetate can be used. Among these organic solvents, toluene is preferred from the viewpoint of the environment during production such as dissolution, coating, drying, and lamination. In addition, the coating liquid concentration of the thermoplastic elastomer dissolved using these organic solvents is as follows:
Although it can be arbitrarily selected depending on the type of the coating machine and the thickness of the obtained layer, it is usually used in a concentration range of 10% by weight to 50% by weight.

As the support having the undercoat layer, a polyethylene terephthalate film is optimal in view of dimensional stability, heat resistance and mechanical performance.
Polypropylene polystyrene and other materials can also be used. Also, a material provided with a release layer on this material to facilitate the work of separating the material from the undercoat layer is useful. This release layer has a thickness of about 0.1 μ〜 to 0.1 μm. A release agent layer of about 2 μm is provided, and a silicone resin, an alkyd resin, or the like can be used as the release agent.

The thickness of the undercoat layer obtained by dissolving the thermoplastic elastomer of the present invention in an organic solvent, coating and drying is from 1 μm to 2 μm.
00μ, preferably 10μ to 100μ. If it is less than 1 μm, the adhesiveness to the photosensitive resin layer may not be sufficient, and sufficient releasability from the material treated with the release agent may not be obtained. On the other hand, if it exceeds 200 μm, there are problems in production such as uneven thickness during production coating and generation of pinholes, which is not preferable.

The undercoat layer made of the thermoplastic elastomer of the present invention contains a coloring agent in such a concentration that the photopolymerization of the photosensitive resin layer is not hindered by the floor formation by back exposure of the photosensitive resin layer. You may. Specifically, CI109, CI50
205, CI 50315, CI 50320, CI 425
95, CI45210, CI45160, CI4251
A color index NO colorant such as 0, CI44090 or the like can be adjusted to an arbitrary concentration and used.

Next, the photosensitive resin composition used in the photosensitive resin laminate of the present invention is not particularly limited according to the intended use, and any photosensitive resin composition which can be subjected to aqueous development can be used. For example, Japanese Patent Application Laid-Open No. Sho 60-212451,
JP-A-60-173055, JP-A-63-8648
JP-A-1-108542, JP-A-1-19773
5, JP-A-2-175702, JP-A-3-2280
No. 60, JP-A-4-3162, JP-A-6-28961
No. 0, JP-A-7-114180 and the like can be used. Note that the aqueous development here is one that can be developed with water or an aqueous solution containing water, and specifically, water, an aqueous solution containing a surfactant,
As the surfactant, alkyl benzene sulfonic acid sodium
Anionic surfactants such as da, nonionic surfactants,
Photosensitive resin composition using an aqueous solution containing a cationic surfactant, an amphoteric surfactant, an alkaline compound such as sodium hydroxide, or an aqueous solution containing alcohols such as methyl alcohol and ethyl alcohol. Can be dissolved or swelled, and can be used alone or as a mixture. When developing with these water or an aqueous solution containing water, the developing temperature is preferably from 25 ° C to 60 ° C.

In the present invention, before obtaining the photosensitive resin laminate of the present invention, it is preferable to previously obtain a photosensitive resin original plate (raw plate) using the photosensitive resin composition. This photosensitive resin original plate has at least a support, an undercoat layer, and a photosensitive resin layer from below, and a release layer between the support and the undercoat layer, and also on the photosensitive resin layer. Preferably has an anti-adhesion layer and a cover film. As a method for obtaining the photosensitive resin original plate, a photosensitive resin composition is prepared by mixing a material having a release agent layer and an undercoat layer on the support and a coverfill material having an anti-adhesion layer in advance. At the center, a method of laminating to a desired thickness and width by a method such as hot press, calendar processing, roll press processing or the like can be adopted. At this time, particularly when an organic solvent is used for producing the photosensitive resin master (raw plate), the solvent content in the photosensitive resin layer is at least 2% by weight or less, preferably 0.5% by weight or less. Lamination with the undercoat layer in the range of 1.5% by weight is particularly preferable for improving the adhesiveness.

The cover film material having an anti-adhesion layer is a cover film having a non-adhesion layer, and specifically includes polyamide-based, polyvinyl alcohol-based, cellulose-based and ethylene-based materials. 1. A resin such as a side resin, a polymer electrolyte resin, or a nylon resin is arbitrarily coated.
A material having an anti-adhesion layer having a thickness of 5 μ to 5 μ can be used.

The elastic material used as the elastic layer in the present invention is not particularly limited. For example, rubber sheets such as raw rubber, vulcanized rubber and synthetic rubber, and soft salt sheet materials And a porous cushion material such as urethane foam. The dimensional accuracy of the elastic body is preferably 10 mm to 0 mm / m in the width direction, more preferably 5 mm to 0 mm / m, particularly 3 mm to 0 mm / m, and 50 mm to 0 mm / 3 m, preferably 3 mm in the length direction.
0 mm to 0 mm / 3 m, particularly preferably 20 mm to 0 mm / 3 m.

In the present invention, the adhesive for bonding the elastic layer and the undercoat layer may be an adhesive having a SP value (solubility parameter) close to the elastic body or the thermoplastic elastomer forming the undercoat layer. Although an agent is preferable, the elastic layer is generally polished and the adhesiveness tends to be improved by an anchor effect. Therefore, it is not always necessary to select an adhesive having a close SP value. Specifically, urethane rubber, chloropyrene rubber, styrene butadiene rubber, nitrile butadiene rubber, natural isoprene rubber, synthetic isoprene rubber, styrene / butadiene / styrene ternary block rubber, styrene / isoprene / styrene ternary block rubber, neoprene rubber , A vinyl acetate resin, a thermoplastic resin such as a vinyl acetate resin / acrylic acid ester copolymer resin, a rubber-based adhesive, a modified resin thereof, and an emulsion-based adhesive. Furthermore, a thermosetting adhesive such as a urethane-based or epoxy-based adhesive, another reaction-based adhesive, or an aerobic adhesive can also be used.

The method of laminating these adhesives is as follows.
On the elastic layer or on the undercoat layer, a brush, a brush, a method of applying by a spray method or the like is generally mentioned. A preferable laminating method is to apply an adhesive in advance on the elastic layer, There is a method in which a photosensitive resin plate having an undercoat layer is brought into close contact with the elastic layer having the adhesive layer while pressing and extruding the plate with a manual rubber roll. In addition, the viscosity of the adhesive at this time is 30 C due to workability when using a manual rubber roll.
Viscosity in the range of PS to 300 CPS, preferably 50 CP
Viscosity in the range of S to 100 CPS is preferred.

[0025]

DESCRIPTION OF THE PREFERRED EMBODIMENTS Various methods can be adopted as a method for obtaining the photosensitive resin laminate of the present invention. In a preferred embodiment, the solvent content is 0.1% by weight to 2% by weight. A subbing layer made of a thermoplastic elastomer, which is a weight percent, is laminated on a support and a release layer, and then a photosensitive resin composed of a water-based developable photosensitive resin composition is laminated, and A support, release layer, subbing layer, photosensitive resin layer, anti-adhesion layer and cover film are prepared in order from the bottom to prepare a photosensitive resin original plate (raw plate). Exposure is performed to cure the floor of the photosensitive resin layer. On the other hand, a multilayer elastic material layer having an adhesive layer is prepared, and the photosensitive resin original plate having the undercoat layer obtained by peeling the support and the release layer from the photosensitive resin original plate and the multilayer elastic material layer are subjected to undercoating. A method of laminating using the above-mentioned means so that the layer and the adhesive layer are adhered to each other, but the present invention is not limited thereto. It may be applied to the layer side.

As described above, the present invention obtained by such a method is a photosensitive resin laminate comprising at least an elastic layer, an adhesive layer, an undercoat layer and a photosensitive resin layer in order from the lower layer. When using the body as a printing plate, it is possible to adopt a method of making a printing plate from a normal photosensitive resin original plate, for example, first image exposure with an original drawing film having an image, and further develop by a developing machine A printing plate (relief) can be created. The active light used for the image exposure is preferably in the wavelength range of 150 to 500 mμ, particularly 300 to 400 mμ. The light source used is a low-pressure mercury lamp, high-pressure mercury lamp, or car light. Bon-arc lamps, chemical lamps, xenon lamps and the like are preferred. The printing plate obtained is, for example, a film, an envelope, a label, a paper bag, a heavy bag, wrapping paper, a cardboard.
The present invention is particularly suitable for corrugated cardboard printing.

[0027]

Next, the present invention will be described in detail with reference to examples, but the present invention is not limited to these examples. In the examples, “parts” means “parts by weight”.
The evaluation method in the embodiment is based on the method described below. (1) Solvent content: a thermoplastic elastomer containing a solvent was coated on a support so as to have a thickness of 50 μm, and then dried under predetermined conditions to form an undercoat layer.
Remove from the support for ² minutes and measure its weight (W ₁ ). Next, the undercoat layer is completely dried (110 ° C. for 1 hour)
The weight (W ₂ ) after the measurement was measured, and (W ₁ −W ₂ ) ×
100 / W ₂ was taken as the solvent content. (2) Adhesion strength test: In accordance with JIS-K6301,
The adhesive strength per inch was determined using a tensile tester manufactured by Toyo Boldwin Co., Ltd. In addition, it shows that adhesiveness is so excellent that the value of adhesive strength is large. (3) Dimensional stability: The degree of curl (deformation) of the relief after development processing was visually determined.

REFERENCE EXAMPLE 1 120 parts of a block copolymer composed of polystyrene / polyisoprene / polystyrene (Creton D-1107 manufactured by Shell Japan KK) was dissolved in 280 parts of toluene, and a coating solution having a solid content of 30% was prepared. Produced. Next, a silicon-treated 100 μm polyethylene terephthalate film (support having a release layer) was coated with a bar coater for 80 minutes.
A material having an undercoat layer whose thickness after drying was adjusted to 50 μm under a drying condition of 3 ° C. for 3 minutes was produced. It was then covered with an embossed polyethylene film to protect the undercoat layer. Using a part of this material layer, the solvent content was measured and found to be 0.5% by weight.

Reference Example 2 A material having an undercoat layer was prepared in the same manner as in Reference Example 1, except that the drying conditions were changed to 70 ° C. for 3 minutes. The solvent content of this undercoat layer was 1.5% by weight.

Reference Example 3 Styrene / isoprene / styrene block copolymer (Creton D-1107 manufactured by Shell Japan K.K.) 120
Was dissolved in 280 parts of toluene, and then 10 parts of 1,6-hexanediol-dimethacrylate was added thereto to give a solid content of 29.3.
% Of a coating liquid, and a material having an undercoat layer similar to that of Reference Example 1 was prepared. The solvent content of this undercoat layer was 0.2% by weight.

Reference Example 4 A photosensitive resin composition was prepared by the following method.
Hexamethylene diisocyanate 21.8 parts, dimethylolpropionic acid 15.4 parts, polytetramethylene glycol (PG-100 Nippon Polyurethane Industry Co., Ltd.)
7.6 parts) and a solution prepared by dissolving 7.6 parts of di-n-butyltin dilaurate in 300 parts of tetrahydrofuran were placed in a 1-liter flask equipped with a stirrer. The reaction was continued for hours. In a separate container, acrylonitrile
Butadiene oligomer (Hycar ATBNX 13
A solution prepared by dissolving 55.3 parts of 00X16 (Ube Industries, Ltd.) in 100 parts of methyl ethyl ketone was added to the above flask while stirring at room temperature. The obtained polymer solution was dried under reduced pressure to remove tetrahydrofuran and methyl ethyl ketone, thereby obtaining a polymer having a number average molecular weight of 21,000. Next, lithium hydroxide was added to a solution of 100 parts of the polymer dissolved in 100 parts of methyl ethyl ketone.
A solution prepared by dissolving 8 parts in 100 parts of methyl alcohol was added at room temperature with stirring, and the mixture was further stirred for 30 minutes to obtain a hydrophilic polymer [1].

10 parts of the above hydrophilic polymer [1], 45 parts of chlorinated polyethylene (H-135 manufactured by Osaka Soda Co., Ltd.) as a hydrophobic polymer, and styrene-butadiene rubber (J
SR1507 Nippon Synthetic Rubber Co., Ltd. 15 parts, butadiene oligoacrylate (PB-A Kyoeisha Yushi Co., Ltd.)
28.5 parts, 1 part of benzyl dimethyl ketal (Irgacure 651, manufactured by Ciba Geigy Co., Ltd.) and 0.5 part of hydroquinone monomethyl ether in toluene 40
And 10 parts of water, and the mixture was kneaded at 105 ° C. using a heating kneader, dissolved and defoamed to obtain a photosensitive resin composition. The residual solvent ratio in this photosensitive resin composition was 1.0% by weight.

Example 1 A material having an undercoat layer having a thickness of 50 μm and a solvent content of 0.5% obtained in Reference Example 1, the photosensitive resin composition obtained in Reference Example 2, and a separately prepared 100 μm A cover having a 2 μ thick anti-adhesion layer made of polyvinyl alcohol on a polyethylene terephthalate mat film having a thickness of 2 μm.
A film is prepared, and a photosensitive resin composition having a thickness of 3 mm having an undercoat layer is formed by molding a photosensitive resin composition at a temperature of 100 ° C. with a roll press machine adjusted to have a total thickness of 3 mm. An original plate (raw plate) was prepared.

Next, a support having a release layer of the photosensitive resin original plate (raw plate) and having a thickness of 100 μm (with a polyethylene terephthalate film attached, an ultraviolet exposure machine (P-113-D manufactured by Dainippon Screen Co., Ltd.) Illuminance of 150 W / m ² ) for 1 minute to form a floor by back exposure and curing.
The support having the release layer is peeled off to expose the photosensitive resin layer having the undercoat layer, and then an elastic body of a rubber sheet material (TW-2 manufactured by Kureha Elastomer Co., Ltd.) having a thickness of 4 mm is formed. While applying a commercially available NR adhesive (manufactured by Shinoda Shoji Co., Ltd.) onto the layer, the photosensitive resin layer having an undercoat layer and the adhesive are brought into close contact with each other by pressing and extruding with a manual rubber roller to form an elastic layer. Then, a photosensitive resin laminate having a thickness of about 7 mm comprising an adhesive layer, an undercoat layer, a photosensitive resin layer, an anti-adhesion layer and a cover film material was prepared. Next, this photosensitive resin laminate was exposed to light for 8 minutes using an ultraviolet light exposure machine, and the adhesive strength was determined using an adhesive strength tester. As a result, 3 kgf / inch was obtained.
It showed the above adhesive strength and did not peel off even when bent at 180 degrees. Next, 300mm ×
After peeling off the cover film on the photosensitive resin laminate having a width of 500 mm, the original film having an image is placed, adhered in vacuum, exposed to the surface for 8 minutes using an ultraviolet exposure machine, and the original film was removed. Then, the alkyl naphthalene sulfonate was removed. A batch type developing machine of a strong rotating brush with neutral water containing 2% by weight of nylon (nylon brush, touch pressure 3 mm, rotation speed 50/20)
development at 40 ° C. for 15 minutes at a depth of 1.9 mm
Was obtained. The resulting relief had no peeling of the image pattern and no curling. Next, aqueous flexo ink for corrugated ball (LOXS, manufactured by Toyo Ink)
When printing was performed using the model printing tester using G), the image pattern did not peel off during printing, and there was no particular problem with printability.

Example 2 Example 1 was repeated except that a 100 μm thick support having a release layer of a photosensitive resin original plate (raw plate) having a thickness of 3 mm was peeled off and back-exposed with an ultraviolet exposing machine. Approximately 7 layers having an elastic layer, an adhesive layer, an undercoat layer, a photosensitive resin layer, an anti-adhesion layer, and a cover film material in the same manner as described above.
A photosensitive resin laminate having a thickness of 2 mm was prepared, and the adhesive strength was determined by the same method as in Example 1. The adhesive strength was 3 kgf / inch or more. When a relief having a-
There was no particular problem in printability without peeling of the image pattern.

Example 3 The procedure of Example 1 was repeated, except that the undercoat layer obtained in Reference Example 2 was used instead of the one obtained in Reference Example 1 to obtain a photosensitive layer. A conductive resin laminate was obtained. As a result, it showed an adhesive strength of 3 kgf / inch or more, and was further developed by the same method as in Example 1 to produce a relief having an image pattern. There was no particular problem.

Example 4 The procedure of Example 1 was repeated, except that the undercoat layer obtained in Reference Example 3 was used instead of the undercoat layer obtained in Reference Example 1. A conductive resin laminate was obtained. As a result, it showed an adhesive strength of 3 kgf / inch or more, and was further developed by the same method as in Example 1 to produce a relief having an image pattern. There was no particular problem.

Example 5 In Example 1, the adhesive was replaced with a commercially available NR adhesive.
A photosensitive resin laminate having a thickness of about 7 mm was prepared in the same manner as in Example 1 except that Diabond DA753 (manufactured by Nogawa Chemical Co., Ltd.) was used.
gf / inch or more adhesive strength, and the dimensional stability of the relief having the image pattern after the development processing is satisfactory.
There was no particular problem in printability without peeling of the image pattern.

Example 6 In Example 1, the adhesive was replaced with a commercially available NR adhesive.
A photosensitive resin laminate having a thickness of about 7 mm was prepared in the same manner as in Example 1 except that Hibon 1920LT (manufactured by Hitachi Chemical Co., Ltd.) was used, and the adhesive strength was determined. The result was 3 kgf / i.
It shows an adhesive strength of nch or more, and the image pattern after development processing
There was no problem in the dimensional stability of the relief having the pattern, and there was no particular problem in the printability without peeling of the image pattern.

Example 7 In Example 1, development was carried out at a developing temperature of 50 ° C. using an automatic developing machine (manufactured by JEOL Ltd.) instead of using a batch developing machine. The depth of the relief was 1.5 mm, and the dimensional stability of the relief having the image pattern was not a problem. The image pattern was not peeled off and the printability was not a problem.

Comparative Example 1 A photosensitive resin laminate (raw plate) having a thickness of 3 mm was prepared using the photosensitive resin composition of Reference Example 2 without the undercoat layer of Reference Example 1. Next, back exposure was performed with an ultraviolet exposure machine in the same manner as in Example 1, and then the photosensitive resin laminate having a thickness of about 7 mm was produced by closely adhering to a support with a commercially available NR adhesive.
Next, when the adhesive strength was determined by an adhesive strength tester in the same manner as in Example 1, it was 0.17 kgf / inch. Next, a relief having an image pattern was prepared by developing in the same manner as in Example 1. When almost all the surface was peeled off from the support, the image pattern was not used for printing.

COMPARATIVE EXAMPLE 2 Using the photosensitive resin laminate (raw plate) having a thickness of 3 mm of Comparative Example 1, Diebond DA753 was used instead of a commercially available NR adhesive.
A photosensitive resin laminate having a thickness of about 7 mm was prepared in the same manner as in Comparative Example 1 except that the above was used, and the adhesive strength was determined by an adhesive strength tester.
Next, development was performed in the same manner as in Comparative Example 1 to produce a relief having an image pattern. When the relief was completely removed from the support, printing was stopped.

Comparative Example 3 Styrene / Isoprene / Styrene Block Copolymer (Creton D-1107 manufactured by Shell Japan K.K.) 120
Was dissolved in 280 parts of toluene, and then 10 parts of 1,6-hexanediol-dimethacrylate was added thereto to give a solid content of 29.3.
% Of a coating liquid, and a material having an undercoat layer similar to that of Reference Example 1 was prepared. Next, a photosensitive resin laminate (raw plate) having a thickness of 3 mm was prepared in the same manner as in Example 1 using the photosensitive resin composition of Reference Example 2, and back-exposed for 1 minute with an ultraviolet exposure machine. After curing, a photosensitive resin laminate having a thickness of about 7 mm was prepared using an organic solvent to adhere and adhere the support and the photosensitive resin layer. The adhesiveness to the support was insufficient and the film was easily peeled off when peeled off by hand, and the production of an image pattern was stopped.

COMPARATIVE EXAMPLE 4 Comparative Example 3 In place of back-exposing a 3 mm-thick photosensitive resin laminate (raw plate) with the undercoat layer material attached thereto, an organic material was exposed after the undercoat layer material was removed and back-exposed. A photosensitive resin laminate having a thickness of about 7 mm was prepared in the same manner as in Comparative Example 3 except that the support was adhered to and adhered to the support with a solvent. Then, surface exposure was performed for 8 minutes using an ultraviolet exposure machine to determine the adhesive strength.
inch. Then, when an image pattern was produced in the same manner as in Example 1, peeling occurred in the finely trimmed portion of the image pattern of the relief. When printing was carried out using this, blurring was recognized in the printing of the part where peeling occurred.

Reference Example 5 The results of Examples 1 to 7 and Comparative Examples 1 to 4 are shown in Table 1 below.

[0046]

[Table 1]

[0047]

The photosensitive resin laminate of the present invention having the above construction is particularly useful for flexographic printing plates comprising an aqueous developing photosensitive resin composition, and is useful for printing on corrugated balls, double bags and the like. Particularly suitable. In addition, it has excellent adhesion to the support and dimensional stability, and can be used for batch developing machines with strong rotating brushes and wide-width automatic developing machines that will be used frequently in the near future. It is a great contribution to the printing industry.

Claims (3)

[Claims] 1. A photosensitive resin laminate comprising at least an elastic layer, an adhesive layer, an undercoat layer and a photosensitive resin layer in order from the lower layer. 2. The photosensitive resin laminate according to claim 1, wherein the undercoat layer is a layer made of a thermoplastic elastomer and has a solvent content of 0.1 to 2% by weight. 3. A photosensitive resin layer having an undercoat layer and an elastic layer having an adhesive layer are laminated so that the undercoat layer and the adhesive layer are in contact with each other. Of producing a photosensitive resin laminate.